WO2012076950A1 - Dépôt électrophorétique de batteries en couches minces - Google Patents

Dépôt électrophorétique de batteries en couches minces Download PDF

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Publication number
WO2012076950A1
WO2012076950A1 PCT/IB2011/002916 IB2011002916W WO2012076950A1 WO 2012076950 A1 WO2012076950 A1 WO 2012076950A1 IB 2011002916 W IB2011002916 W IB 2011002916W WO 2012076950 A1 WO2012076950 A1 WO 2012076950A1
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WIPO (PCT)
Prior art keywords
separator
tfb
solid
substrate
electrode
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PCT/IB2011/002916
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English (en)
Inventor
Diana Golodnitsky
Emanuel Peled
Menachem Nathan
Gilat Ardel
Hadar Mazor-Shafir
Roni Hadar
Svetlana Menkin-Bachbut
Tania Ripenbein
Kathrin Freedman
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Ramot At Tel-Aviv University Ltd.
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Application filed by Ramot At Tel-Aviv University Ltd. filed Critical Ramot At Tel-Aviv University Ltd.
Priority to EP11808327.8A priority Critical patent/EP2647066A1/fr
Priority to JP2013542623A priority patent/JP2014500597A/ja
Priority to US13/988,337 priority patent/US9249522B2/en
Publication of WO2012076950A1 publication Critical patent/WO2012076950A1/fr
Priority to US14/986,637 priority patent/US20160118684A1/en

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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • H01M10/052—Li-accumulators
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Definitions

  • Embodiments disclosed herein relate generally to energy storage devices and more particularly to electrophoretic deposition (EPD) of thin film batteries (TFBs) in both two-dimensional (2D) and three-dimensional (3D) configurations.
  • EPD electrophoretic deposition
  • TFBs thin film batteries
  • BACKGROUND TFBs comprise a "stack" of two, one negative (“anode”) and one positive
  • each electrode may range from sub- micrometer (“sub-micron”) to a few microns.
  • the thickness of the separator may range from sub-micron to a few tens of microns.
  • the stack is formed on a substrate. If one or both electrodes are not sufficiently electronically conductive, thin film current collectors (“CC”s) are provided to facilitate electron current flow in an external circuit. One such CC is formed on the substrate prior to the formation of the TFB stack.
  • 3D-TFBs as disclosed for example in US patent No. 6,197,450 to Nathan et al., are formed inside perforations (through-holes or cavities) of a substrate as well as on any remaining original (planar) surface of the substrate. Each perforation may include a partial or full stack of concentric layers forming a "concentric microbattery" or "CMB".
  • CMB Concentric microbattery
  • Such 3D-TFBs combine the known advantages of 2D-TFBs with an order of magnitude and more increase in power and energy per footprint (original substrate area).
  • a general known problem with CMBs is the difficulty of forming a solid separator using wet chemistry. Also, known art does not teach electrochemical deposition of a full three layer battery stack.
  • Electrophoresis refers to the motion of charged particles in a liquid under an applied electric field. Electrophoresis can be used to deposit materials in the form of thin films (layers), coatings and bulk products. The deposition process is commonly termed “electrophoretic deposition” (EPD). Reviews of EPD include those by Van der Biest and Vandeperre, Ann. Rev. Mater. Sci., 29 (1999) 327-352 and by Corni et al., J. Europ. Ceram. Soc, 28 (2008) 1353-1367. The EPD of layers faces a hurdle in the requirement that the solid to be deposited be available as a colloidal suspension or powder with grains smaller that a required layer thickness.
  • EPD has been used to produce bulk battery electrodes, see e.g., Kanamura et al., Electrochemical and Solid-State Letters, 3 (2000) 259-262, and Kanamura et al., J. Power Sources, 97-98 (2001) 294-297.
  • the use of EPD to prepare film (thick or thin) battery components has been extremely limited, and applied mainly to positive electrodes (cathodes).
  • Structures and materials investigated include thick films of LiNio . sMni 5 ⁇ 4 [Caballero et al., J. Power Sources 158 (2005) 583-590] and relatively thin films of Li 4 Ti50i 2 [Sugiura et al., Functional Mater. Lett. 2(1) (2009) 9-12].
  • a general concern and trend in the EPD of TFB electrodes it to make them dense (as opposed to porous).
  • Electrophoretic assembly of electrochemical devices is also disclosed by Chiang et al. in US patent No. 7,662,265. Their methods requite always use of two current collectors ("terminals") for EPD of mutually repulsive electrodes, and cannot be used to EPD TFBs on a single current collector.
  • Embodiments disclosed herein provide methods to produce partial or full thin- film battery stacks on both planar (2D) and 3D substrates using EPD.
  • EPDd means "electrophoretically deposited”.
  • Layers of a battery stack are EPDd in sequence on a single electronically conductive substrate which can be either in bulk form or in film form.
  • the single conductive substrate also serves as a first current collector.
  • a first polarity electrode and a separator are EPDd in sequence to form a two-layer stack, with a second, opposite polarity electrode added to complete a TFB stack.
  • a "three-layer" electrode-separator-electrode battery stack is EPDd in sequence on a single current collector.
  • the separator includes an electronically insulating inorganic porous solid.
  • porous solid refers to a continuous solid structure having porosity of varying degrees. This definition does not inorganic solid powders dispersed in an organic matrix, where the "solid" phase is not continuous.
  • the porous solid provides pathways for cations (e.g. protons), which lose their positive charge (reduce) on the first polarity electrode.
  • the inorganic porous solid is an oxide. In some embodiments, the inorganic porous solid is a glass-ceramic.
  • the inventors prepared glass- ceramic powders of small enough size (diameter) for EDP of separators inside through- holes having aspect ratios (AR) of length to diameter greater than 1 and diameters of exemplarily 50 ⁇ . Electrochemical deposition of conformal thin films of glass-ceramics inside holes with AR greater than 1, greater than 5 and even greater than 10, wherein the hole diameters are on the order of a few tens of microns, is extremely difficult.
  • the inventors are unaware of any successful EPD of a glass-ceramic layer inside through holes, or, for that matter, on planar substrates The inventors managed to overcome significant technical difficulties in developing EDP processes for such layers.
  • the first polarity electrode is a cathode and the second polarity electrode is an anode. In some embodiments, the order of the electrodes is reversed. In some embodiments, the EPDd two-layer or three-layer structures are impregnated with an ion-conductive liquid (electrolyte).
  • the single conductive substrate is a thin-film current collector formed on a fully-perforated substrate (having through-holes as e.g. in US 6,197,450) or on a semi-perforated substrate (with non- through-holes, as e.g. in US 7,772,800).
  • through-hole indicates a perforation of any shape which extends between and penetrates two opposite and substantially planar surfaces bounding a substrate. Non-limiting examples of through-holes may be found in Averbuch et al., J. Power Sources, 196 (2011) 1521-1529.
  • a TFB in which a three-layer stack is inserted in substrate holes is a "full-3D" TFB.
  • a TFB in which only two layers of a three- layer stack are inserted in substrate holes is a "semi-3D" TFB.
  • a separator and/or second electrode may be EPDd on a first electrode which is formed by another method.
  • a separator and/or an anode may be EPDd on an electrodeposited CuS or MoS cathode, on both planar and 3D perforated substrates.
  • an EPDd TFB disclosed herein is a Li-ion TFB.
  • the cathode is made of a lithiated metal phosphate.
  • the lithiated metal phosphate is LiFeP0 4 (henceforth referred to as "LFP").
  • the separator is in the form of a composite solid thin-film electrolyte or a composite ceramic hybrid electrolyte.
  • ionic conductivity may be provided by impregnating an inorganic porous solid with a liquid, for example EC/DEC 1M LiPF6.
  • the porous solid is sintered after the formation of the anode layer, with the goal of decreasing porosity and grain-boundary resistance.
  • the sintering is applied to the entire battery structure.
  • the anode includes graphite or meso-carbon micro-beads (MCMB), or nanotubes. In other embodiments, the anode includes nano-silicon. In some embodiments, the anode and/or the cathode may be co-deposited with an electronically conducting material, such as carbon or/and graphite powders.
  • Particles useful in the EPD of TFB structures described herein can be in the nanometer to micrometer range. Large particles can be ball-milled to small diameters, down to submicron and even nanometer range.
  • an EPDd layer includes two or more types of different micro- and nano-sized particles.
  • the particle size is less than ⁇ . In some embodiments, the particles size is less than ⁇ . In some embodiments, the particle size is less than lOOnm.
  • the anode and/or cathode powders may be pre-coated by one or more (e.g. up to 10) monolayers of carbon prior to EPD.
  • EPDd 2D-TFBs and 3D-TFBs are coated and sealed with an EPDd PEEK packaging layer.
  • Additional polymers that can be EPDd to serve as battery packaging layer include Nylon-MXD6 (a copolymer of m-Xylyenediamine and Adipic acid), PVDC (plasticized Vinylidene Chloride copolymer) and EVOH copolymer (Ethylene Vinyl Alcohol copolymer).
  • 2D-TFBs may be formed on large (a few square inches to a few square meters) to very large (a few tens of square meters) surfaces, which need not be flat.
  • Such 2D-TFBs may be formed on any conductive surface or non-conductive surface coated with a conductive layer which serves as current collector/deposition electrode.
  • Suitable positive electrode (cathode) materials include ordered rock-salt compounds such as LiCo0 2 , LiNi0 2 , Li(Al, Ni, Mn)0 2 , LiMn0 2 , and solid solutions or doped combinations thereof; spinel structure compounds such as LiMn 2 04 and its doped counterparts or solid solutions with other metal oxides; ordered olivines such as LiFeP0 4 , LiMnP0 4 , LiCoP0 4 , and their doped counterparts or solid solutions; and other ordered transition metal phosphates such as those of so-called Nasicon structure type and their derivatives and related structures.
  • ordered rock-salt compounds such as LiCo0 2 , LiNi0 2 , Li(Al, Ni, Mn)0 2 , LiMn0 2 , and solid solutions or doped combinations thereof
  • spinel structure compounds such as LiMn 2 04 and its doped counterparts or solid solutions with other metal oxides
  • ordered olivines such as LiFeP0 4 ,
  • Suitable negative electrode (anode) materials include compounds such as graphitic or disordered carbons; metal oxides that intercalate lithium such as Li 4 Ti50i 2 spinel and its derivatives; and other metal oxides or their solid solutions that undergo intercalation or displacement reactions such as tin oxide, indium tin oxide, or first-row transition metal oxides; and crystalline or amorphous metals and alloys of metals or metalloids such as Si, Al, Zn, Sn, Ag, Sb, and Bi.
  • Suitable composite ceramic hybrid electrolyte materials include ceramic powders like Zr0 2 , Zr 2 0 3 , Si0 2 , Al 2 0 3i LiA10 2 and polymer binders like PEO, polyethylenimine (PEI), polyvinyldiene fluoride (PVDF), PEG, PMMA, methylcellulose, alkyd resin, dewaxed shellac, polyvinyl butyral (PVB), polyvinyl alcohol (PVA) and poly(dimethyldiallylammonium chloride) (PDDA).
  • the ceramic material is impregnated with a liquid electrolyte typically used for lithium-ion batteries.
  • the liquid electrolyte may be LiPF 6 :EC:DEC.
  • Suitable inorganic solid separator materials include lithium-ion conductive glasses such as lithium zirconate, lithium aluminate, lithium silicate, LiCl-Li 2 0-Si0 2 -P 2 05 i LiCl- Li 2 0-Si0 2 -P 2 05, sulfide-based glasses like Li 2 S-SiS 2 -Al 2 S 3 and Li 2 S-SiS 2 -P 2 S5, Li 2 S-SiS 2 -Li 3 N, lithiated boron oxide glasses of the family xLi 2 0-B 2 0 3 and lithium ion conducting glass ceramics like Li 2 0-Al 2 0 3 -Si0 2 -P 2 05-Ti0 2 -Ge0 2 and Li 2 0-Al 2 0 3 -Si0 2 - ⁇ 2 ⁇ 5 - ⁇ ⁇ ⁇ 2 ⁇
  • the solid electrolyte layers are preferably 1 to 10 ⁇ thick to eliminate high
  • Suitable solvents for use in the EPD of various materials may be found for example in Table 3 of L. Besra and M. Liu, Progress in Materials Science, 52 (2007) 1- 61.
  • the electrophoretic deposition may be enhanced by use of additives.
  • Useful additives include but are not limited to conductive particles that increase the electrical conductivity of the deposited material, such as conductive carbon, metallic particles, or conductive polymer dispersions, or binders that improve the adherence of the deposited particles to each other or to a current collector.
  • conductive particles that increase the electrical conductivity of the deposited material
  • binders that improve the adherence of the deposited particles to each other or to a current collector.
  • Other exemplary additives which may be used for this purpose are described for example in US 7,662,265.
  • FIG. 1 is a low magnification SEM view of a YSZ separator EPDd on a previously EPDd LFP cathode in a planar configuration
  • FIG. 2 shows high resolution SEM views at different magnifications of the YSZ layer in FIG. 1;
  • FIG. 3A shows charge-discharge curves of an assembly of EPDd planar LFP cathode/ YSZ LiPF6 EC:DEC VC tested in a coin cell configuration with a Li foil serving as anode;
  • FIG. 3B shows cycling results of the assembly in FIG. 3A
  • FIG. 4A shows an SEM image of a YSZ-PEI membrane deposited by EPD on a previously EPDd MCMB anode in a planar configuration
  • Fig. 4B shows SEM images of YSZ-PEI membranes EPDd from an acidic suspension (pH2) containing 10 PEI without iodine;
  • FIG. 5 shows SEM images of LiA10 2 -PEG membranes EPDd on a previously EPDd MCMB anode
  • FIG. 6A shows charge-discharge curves of an assembly of EPDd planar assembly
  • FIG. 6B shows cyclability data for the MCMB/(LiA102)-15 PEG LiPF6 EC: DEC/Li cell in FIG. 6A;
  • FIG. 7 shows details of the layers in a cross section of an EPDd three-layer LFP
  • FIG. 8 shows a tilted cross-section SEM view of a perforated 3D Si substrate coated with Au and an EPDd two-layer LFP-YSZ (PEI) structure;
  • FIG. 9A shows polarization curves of 2D and semi-3D cells with EPDd LFP cathode modified with CuS;
  • FIG. 9B shows cyclability data of 2D and semi-3D cells with EPDd LFP cathode modified with CuS.
  • the conductive substrate may be a metal or a thin-film current collector deposited on a non-conducting substrate (e.g. plastic or glass) or on a semiconductor substrate (like silicon).
  • an electrode may be electrically conductive enough to serve as current collector.
  • a second current collector is provided to form a full energy storage cell, which can be packaged in various packages.
  • the separator includes an inorganic porous solid, which, as mentioned, provides pathways for cations which reduce on the first EPDd electrode.
  • the porous solid is impregnated with an ion-conductive electrolyte to provide a "composite ceramic electrolyte".
  • the electrolyte may be LiPF 6 :EC:DEC with a 2% volume VC (vinylene carbonate) solution, or a N-methyl-N- propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 13 TFSI) RT ionic liquid (IL) and LiTFSI salt.
  • the impregnation is carried out after the deposition of the entire battery stack.
  • the separator is a composite solid thin-film electrolyte which includes Li ion conducting, but electronically non-conducting crystalline materials (such as oxide perovskites, Lao . sLio . sTiOs, thio-LISICON, Li 3 25Ge0.25P0.75S4, glass-ceramics, glassy materials (e.g. Li 2 S-SiS 2 -Li 3 P0 4 ), Lii 0 GeP 2 Si 2 , lithium sulfide, lithium iodide, lithium nitride and/or a mixture thereof.
  • Li ion conducting, but electronically non-conducting crystalline materials such as oxide perovskites, Lao . sLio . sTiOs, thio-LISICON, Li 3 25Ge0.25P0.75S4, glass-ceramics, glassy materials (e.g. Li 2 S-SiS 2 -Li 3 P0 4 ), Lii 0 Ge
  • glass ceramic systems useful as ion-conducting separators exist, for example the Li 2 0 x ⁇ 2 ⁇ 3 x nSiC -system (LAS-system), the MgO x ⁇ 2 ⁇ 3 x nSiC - system (MAS -system) and the ZnO x ⁇ 2 ⁇ 3 x nSiC -System (ZAS-system).
  • LAS-system Li 2 0 x ⁇ 2 ⁇ 3 x nSiC -system
  • MAS -system MgO x ⁇ 2 ⁇ 3 x nSiC - system
  • ZnO x ⁇ 2 ⁇ 3 x nSiC -System ZnO x ⁇ 2 ⁇ 3 x nSiC -System
  • all separators are porous (i.e. include a porous solid) in order to enable further EPD of a second electrode.
  • the EPDd first electrode can serve as a deposition electrode for the EPD of an electronically insulating and ionically conducting separator.
  • the first electrode/separator stack was found able to serve as a deposition electrode in the EPD of the second electrode. This is enabled by the porosity of the separator solid, which allows cation (proton) motion to the first electrode.
  • the porous separator was EPDd as a conformal layer on a first electrode previously EPDd inside holes of a perforated substrate.
  • the second electrode could be EPDd as a conformal layer over the conformal separator above, i.e. all three layers could be EPDd in sequence inside perforations. That is, concentric microbatteries (CMBs) inside holes could be formed entirely by EPD.
  • CMBs concentric microbatteries
  • the porous separator EPDd inside holes could be sintered and used for ionic conduction without impregnation by an ionically conducting liquid.
  • the following examples illustrate the sequential EPD of two-layer and three-layer TFB stacks on a single conductive substrate in both 2D and 3D configurations, and 2D- TFBs and 3D-TFBs obtained by EPD.
  • Example 1 Two-layer LiFePC>4 / Zr0 2 (8% Y 2 Os) 2 stack on a planar substrate
  • FIG. 1 shows a low magnification SEM view of the YSZ layer, having a porosity of between 40-50%.
  • FIG. 2 shows high-resolution SEM images of the same layer at different magnifications.
  • LFP powder (Hydro Quebec, Canada), black-pearl carbon (BP) and PVDF were dispersed in an acetone solution with 0.28mg/L.
  • the weight percentage ratio of LFP:BP:PVDF was (91:4:5 %).
  • 0.4% v/v polymer triton-X 100 (TTX, (Ci 4 H 22 0(C 2 H 4 0)n) was added to the dispersion.
  • Black-pearl carbon and PVDF were used as conducting and binding materials, respectively.
  • the modification of the film with TTX caused smoother and more homogeneous deposition during the EPD process.
  • the addition of iodine produces charged particles (protons) in the solution through chemical reaction of I 2 with acetone.
  • the reaction may be written as follows: CH 3 COCH 3 ⁇ CH 3 C(OH)CH 2
  • a nickel disk was used as a substrate (working electrode) and a graphite plate was used as a counter electrode.
  • the constant voltage applied between the two electrodes was set at 60V for 60 seconds.
  • the mass of the EPDd LFP deposit was 9 mg.
  • the YSZ membrane was prepared by cathodic EPD on the LFP cathode (which served as working electrode), using a deposition bath with the following composition: 250ml Ethanol, 0.7gr YSZ, 4ml Acetone, 2ml water, 0.4 ml Acetylacetone, 0.027gr Iodine and 0.0105gr PEI (PolyEthylene Imine).
  • the graphite plate served as counter electrode.
  • the working distance between the electrodes was 15mm.
  • the deposition solution preparation was carried in two steps: preparation of solution 1 containing 150ml Ethanol, 0.4ml Acetylacetone and 0.7gr YSZ in one container and stirring overnight; and preparation of solution 2 containing 100ml Ethanol, 2ml de- ionized water, 4ml acetone and 0.027gr iodine and stirring for a few minutes. Solutions 1 and 2 where then mixed and placed in an ultrasonic bath. EPD was carried out at room temperature (RT) and atmospheric conditions using a Keithley 2400 source-meter. The addition of iodine produced protons in the solution, as explained above. Some of the protons were adsorbed on the Zr0 2 particles, rendering them positively charged.
  • the addition of PEI to the solution helped to obtain a smoother, adherent film.
  • the YSZ deposition was carried out at a constant current of 1.6 niA/cm for 10 minutes, and resulted in a highly adherent conformal deposit on the LFP cathode.
  • a LFP cathode/YSZ-PEI assembly EPDd as above was tested in a coin cell configuration, with a Li foil serving as anode.
  • the YSZ-PEI membrane was impregnated with LiPF 6 :EC:DEC electrolyte with an added 2% volume VC solution.
  • the VC solution improves solid electrolyte interphase (SEI) properties.
  • SEI solid electrolyte interphase
  • the configuration was sealed in a stainless steel coin cell.
  • the Li/ YSZ / LFP cells were cycled at RT using a Maccor series 2000 battery test system. Charge-discharge curves and cycling results are shown in FIGS. 3A and 3B.
  • the voltage cut-off was 2.8 to 3.5V, with a charge/discharge at a current density of 75 ⁇ /cm 2.
  • the cells provided 0.1-0.2 mAh/cm 2 capacity for more than 50 reversible cycles.
  • the Faradaic efficiency was close to 100%.
  • Example 2 Two-layer LiFePC>4 / LiA10 2 stack on a planar substrate
  • a two-layer LFP / LiA10 2 stack was prepared by EPD on a Ni planar current collector substrate.
  • the LFP cathode was deposited as in Example 1.
  • the LiA10 2 membrane was then deposited by cathodic EPD on the LFP, using a deposition bath with the following composition: 250ml Ethanol, 0.7gr LiA10 2 , 4ml Acetone, 2ml water, 0.4ml Acetylacetone, 0.027gr Iodine and 0.0105gr PEI.
  • the deposition solution preparation was carried in two steps: preparation of solution 1 containing 150ml Ethanol, 0.5ml Acetylacetone and 0.8gr LiA10 2 in one container with overnight stirring, and preparation of solution 2 containing 100ml Ethanol, 3ml deionized water, 4.5ml acetone and 0.035gr iodine with stirring for a few minutes. Solutions 1 and 2 where then mixed and placed in an ultrasonic bath for 20 minutes. 0.0105gr of PEI was then added to the mixed solution.
  • the EPD of LiA10 2 was carried out at RT under atmospheric conditions using a Keithley 2400 source-meter, with the LFP as working electrode and a graphite plate distanced 15 mm therefrom as counter electrode.
  • the LiA10 2 EPD was carried out at a constant current of 1.6 mA/cm for 10 minutes. The result was a highly adherent conformal LiA10 2 deposit.
  • LiImide:PEG500 electrolyte was then dripped onto the surface of the LiA10 2 and the materials dried.
  • the two-layer LiFeP0 4 / LiA10 2 stack was soaked in LiImide:PEG500 liquid electrolyte under vacuum for 30 min and left overnight in the solution.
  • An assembly of EPDd LFP cathode/Li AlO 2 -LiImide:PEG500 was tested in a coin cell configuration with a Li foil serving as anode. The configuration was sealed in a stainless steel coin cell.
  • the Li/LiA10 2 /LFP cells were cycled at RT using a Maccor series 2000 battery test system and exhibited the typical behavior of a Li TFB.
  • Example 3 Two-layer MCMB / YSZ stack on a planar substrate
  • a MCMB anode was deposited by cathodic EPD on a Ni current collector using a deposition bath with the following composition: 250ml Ethanol, 0.9gr MCMB, 4.5ml Acetone, 2ml water, 0.5ml Acetylacetone, 0.05gr Iodine and 0.008gr PEI.
  • the deposition solution preparation was carried in two steps: preparation of solution 1 containing 150ml Ethanol, 0.4ml Acetylacetone and 0.7gr MCMB in one container with stirring for a few minutes; and preparation of solution 2 containing 100ml Ethanol, 2ml deionized water, 4ml Acetone and 0.05gr Iodine with stirring for a few minutes.
  • FIG. 4A shows SEM images of two-layer MCMB-membrane stack with a YSZ-PEI membrane EPDd from an acidic suspension (pH 2) containing 10 PEI.
  • the YSZ-PEI deposition was performed at 200V using 5-10 pulses of 10s each.. Lowering of the pH enabled using a solution without iodide for EPD.
  • Example 4 Two-layer MCMB / LiA10 2 stack on planar substrate
  • a MCMB anode was deposited by cathodic EPD on a Ni current collector as in Example 3.
  • a LiA10 2 membrane was deposited on the MCMB anode using the electrolyte described in Example 2.
  • 10% (v/v) PEGDME was added to the suspension.
  • the membrane was deposited by pulse potential cathodic EPD.
  • the applied voltage was 100V and the deposition was carried out stepwise. The duration of each step was 30 sec. Between the deposition steps, the sample was removed from the suspension and dried under ambient conditions until complete evaporation of the solvent.
  • FIG. 5 shows SEM views of LiA10 2 -based membranes deposited by EPD from suspensions containing two different concentrations (15% and 50%) of PEG-polymer binder.
  • a wide concentration range of polymer can be used in the suspension. Better uniformity and porosity can be achieved when the suspension contains 15%PEG. TGA tests indicated that the polymer concentration in the EPD layers did not exceed 3.5-5.5%.
  • FIG. 6A shows a discharge curve of the Li/ LiA10 2 -15% PEG /MCMB cell.
  • FIG. 6B shows cyclability data for this cell. The comparison of the cell voltage profile with that of a similar cell including a commercial Celgard membrane proves the feasibility of using the disclosed membrane for Li-ion cells.
  • Example 5 Three-layer LiFeP0 4 / YSZ/ MCMB stack on planar substrate
  • a three-layer LFP / YSZ / MCMB stack was prepared by EPD on a planar Ni current collector. All three layers were EPDd in sequence on the single Ni current collector. The cathode and separator layers were EPDd as in Example 1. The MCMB anode was subsequently deposited by cathodic EPD on the YSZ using a deposition bath described in Example 3. The Ni/LFP/ YSZ assembly was used as working electrode and a graphite plate was used as a counter electrode, with a working distance of 15mm between the electrodes. The inventors found that unexpectedly, while YSZ is an electronically non-conductive separator, its high porosity (here ca. 60%) enables high proton mobility inside pores and hydrogen evolution reaction on the electronically conducting Ni/LFP surface, assisting the EPD of the MCMB layer. The MCMB is electronically conductive enough to also serve as an anode current collector.
  • FIG. 7 shows a cross section of the EPDd three-layer LFP /YSZ/ MCMB stack.
  • the separator thickness is roughly 110-120 ⁇
  • the thickness of the MCMB anode is roughly 80-90 ⁇
  • the thickness of the cathode LFP is roughly 70-80 ⁇ .
  • the thickness of each layer can be controlled by (among others) controlling the deposition time, and can be made much thinner.
  • the YSZ separator may be made thinner than 10 ⁇ , thinner than 5 ⁇ and even thinner than 2 ⁇ .
  • Example 6 Two-layer LiFePC>4 / YSZ stack on perforated (3D) substrate
  • a two-layer LFP / YSZ stack was prepared by EPD on a 3D perforated substrate which had a previously electrolessly deposited thin (1-2 ⁇ ) Au layer on all available surfaces.
  • a tilted SEM picture of the stack is shown in FIG. 8.
  • the two-layer LFP / YSZ stack was EPDd inside 50 ⁇ diameter holes in a 500 ⁇ thick silicon substrate as well as on all remaining planar surfaces.
  • the hole aspect ratio (length/diameter) was 10: 1.
  • the preparation of the solution and deposition of the LFP were performed as in Example 1 , except that two graphite plate counter electrodes were positioned in parallel, one on each side of the Si substrate, each at a distance of ca. 15mm from a respective surface of the Si.
  • the preparation of the solution and the deposition of the YSZ layer were also performed as in Example 1.
  • the thickness of the separator so formed was about ⁇ .
  • the 3D LFP / YSZ stack was tested in a coin cell configuration with a Li foil serving as anode. This configuration forms a so-called "semi-3D" TFB.
  • the Li foil was brought into an intimate contact with the YSZ on the top surface of the substrate.
  • the electrolyte was LiPF 6 :EC:DEC with a 2% volume VC solution.
  • the configuration was sealed in a stainless steel coin cell.
  • the Li/ YSZ / LFP cells were tested at RT using a Maccor series 2000 battery test system. A stable OCV of 3.6V was measured. The testing proved that the assembly performs as a Li battery.
  • Example 7 Three-layer LiFeP0 4 / YSZ / MCMB stack on perforated (3D) substrate
  • a three-layer LFP / YSZ/ MCMB stack was prepared by EPD on a 3D perforated substrate.
  • a LFP / YSZ stack was prepared on a Ni coated Si perforated substrate as in Example 1.
  • Two graphite plate counter electrodes were positioned in parallel, one on each side of the Si substrate, each at a distance of ca. 15mm from a respective surface of the Si.
  • a MCMB anode was subsequently deposited by cathodic EPD on the YSZ as in Example 3.
  • the MCMB was electronically conductive enough to also serve as anode current collector.
  • the resulting structure was one of a concentric electrode / separator / electrode stack formed in each hole in the perforated substrate and also formed on the remaining planar surfaces of the substrate. This configuration forms a so-called "full-3D" TFB.
  • Example 8 Improvement of LiFePC>4 conductivity
  • a topcoat material with high mixed electron/ion conductivity exemplarily copper sulfide (CuS)
  • CuS copper sulfide
  • EPD electrochemically synthesized on the EPDd LFP cathode with the use of procedure described in H. Mazor et al., Electrochemical and Solid-State Letters, 12, (2009), A232-A235.
  • the CuS was deposited on both 2D and 3D Si substrates over the LFP.
  • Planar and semi-3D cells comprising an Au cathode current collector, an EPDd LFP cathode modified by CuS layer, a Celgard separator soaked in commercial electrolyte (LiPF 6 in 1 :1 EC:DEC) and a lithium anode were assembled and tested.
  • a semi-3D cell exhibited a 1.5-2.3mAhcm " (per battery footprint) reversible capacity.
  • the capacity values were stable for 100 cycles with a degradation rate of 0.01% capacity loss per cycle.
  • FIG.9B shows polarization curves of 2D and semi-3D cells with EPDd LFP cathode modified by CuS. Both cathodes were deposited under similar conditions and both contained LFP, black-pearl carbon, PVDF binder (ratio 91:4:5%(w/w)) and TTX- 100. The pulse duration was one second followed by a rest period of 20 seconds. As can be seen from the graph, the transition from 2D to 3D architecture is followed by an increase in maximum current-density capability from 30 to 75mAcm " .
  • the semi-3D cells with CuS-coated modified LFP electrodes were able to provide more than 85mAcm " current density and 204mWcm " peak power per battery footprint, a 24% increase over the semi-3D non-CuS coated LFP cell and a significant enhancement in comparison with the 2D LFP cell.
  • Example 9 Three-layer LiFeP0 4 / LizO-AhC SiC ⁇ Os-TiCh / MCMB stack on planar substrate
  • a 3-layer planar LFP/ Li 2 0-Al 2 03-Si0 2 -P 2 0 5 -Ti0 2 /MCMB structure with solid electrolyte was EPDd on a single Ni current collector.
  • the LFP layer was deposited as in Example 1.
  • the Li 2 0-Al 2 0 3 -Si0 2 -P 2 0 5 -Ti0 2 is a glass-ceramic available commercially in powder form from OHARA Ltd, and described exemplarily in US patent application 20080289365.
  • the powder was ball-milled for 24 hours before preparation of the suspension for EPD.
  • the Li 2 0-Al 2 03-Si0 2 -P 2 05-Ti0 2 was then EPDd under the same conditions as the LiAlC in the Example 2.
  • the MCMB anode was then EPDd as in Example 3 on the LFP/glass-ceramic stack.
  • Example 10 Three-layer MCMB/ LiAlCVLFP stack on perforated Si substrate coated by Ni current collector
  • a MCMB anode was deposited by cathodic EPD on a 3D-perforated Si substrate coated by Ni current collector. The thickness of nickel layer was 5 ⁇ to eliminate co- intercalation of lithium to the silicon substrate trough pits of Ni.
  • a MCMB anode was deposited as in Example 3.
  • a LiAlC membrane was deposited on the MCMB anode using the electrolyte described in Examples 2 and 4.
  • the LFP cathode was EPDd on the LiA10 2 membrane-PEG membrane using the procedure described for LFP in the Example 1.
  • Example 11 EPD of PEEK protective and pre-packaging layer
  • a polyaromatic, semicrystalline thermoplastic polymer, Polyetheretherketone (PEEK),(-C 6 H4-0-C 6 H4-0-C 6 H 4 -CO-)n was electrophoretically deposited on the LFP/ Li 2 0-Al 2 0 3 -Si0 2 -P 2 0 5 -Ti0 2 /MCMB structure prepared as in Example 9.
  • a Ni coated substrate was placed in the EPD bath as a cathode between two graphite plates connected to the anode CC.
  • PEEK suspensions were prepared by magnetic stirring of 2g PEEK powder (Victrex, UK) in 250mL ethanol. The stirring was conducted for 3 hours, followed by 30 min ultrasonic treatment.
  • the suspension was mixed with the second bath containing 4ml Acetone, 2ml water, 0.5 ml Acetylacetone and 0.04gr Iodine. An additional 30 min ultrasonic treatment was then carried out. A small area surrounding the current collector contacts was shielded. PEEK EPD was carried our at an applied voltage was 140V stepwise with 30 sec per step. The as-deposited PEEK layer was porous. The final PEEK/Ni/LFP/Li 2 0-Al 2 0 3 -Si0 2 -P 2 0 5 -Ti0 2 /MCMB / PEEK structure was dried in vacuum at lOOC for 7 hours. After drying, the sample was heated at 350C for 20 minutes to provide a dense PEEK polymer coating, which serves as a protective and prepackaging layer of the battery to eliminate penetration of moisture and oxygen.

Abstract

L'invention porte sur des procédés de formation de structures de batterie en couches minces (TFB) à trois couches par dépôt électrophorétique séquentiel (EPD) sur un unique substrat conducteur. Les TFB peuvent être bidimensionnelles ou tridimensionnelles. L'EPD séquentiel comprend un EPD d'une première électrode de batterie suivi par un EPD d'un séparateur poreux sur la première électrode et par un EPD d'une seconde électrode de batterie sur le séparateur poreux. Dans certains modes de réalisation d'une TFB Li ou Li-ion, le séparateur comprend un solide conducteur Li-ion. Dans certains modes de réalisation d'un TFB Li ou Li-ion, le séparateur comprend un solide poreux inorganique rendu conducteur des ions par imprégnation avec un liquide ou un polymère. Dans certains modes de réalisation, les TFB sont revêtues et scellées de manière étanche par une couche PEEK déposée par dépôt électrophorétique (EPD).
PCT/IB2011/002916 2010-12-05 2011-12-05 Dépôt électrophorétique de batteries en couches minces WO2012076950A1 (fr)

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FR2982083B1 (fr) * 2011-11-02 2014-06-27 Fabien Gaben Procede de realisation de films minces d'electrolyte solide pour les batteries a ions de lithium
JP6108249B2 (ja) * 2013-10-31 2017-04-05 エルジー・ケム・リミテッド 正極活物質、この製造方法、及びこれを含むリチウム二次電池
KR101805545B1 (ko) * 2013-11-11 2017-12-07 삼성에스디아이 주식회사 전극 조립체 및 이를 채용한 이차 전지
DE102013226064A1 (de) * 2013-12-16 2015-06-18 Robert Bosch Gmbh Verfahren zur Herstellung einer Funktionsschicht für eine Lithium-Zelle
FR3023417B1 (fr) * 2014-07-01 2016-07-15 I-Ten Batterie entierement solide comprenant un electrolyte solide et une couche de materiau polymere solide
DE102014117640A1 (de) * 2014-12-01 2016-06-02 Schott Ag Elektrisches Speichersystem mit einem scheibenförmigen diskreten Element, diskretes Element, Verfahren zu dessen Herstellung sowie dessen Verwendung
JP6868335B2 (ja) * 2015-01-12 2021-05-12 アイメック・ヴェーゼットウェーＩｍｅｃ Ｖｚｗ 固体バッテリおよび製造方法
EP3353844B1 (fr) 2015-03-27 2022-05-11 Mason K. Harrup Solvants entièrement inorganiques pour électrolytes
US9755221B2 (en) 2015-06-26 2017-09-05 Palo Alto Research Center Incorporated Co-extruded conformal battery separator and electrode
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KR102553859B1 (ko) * 2017-01-02 2023-07-11 3디베터리즈 리미티드 에너지 저장 장치 및 시스템
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WO2021205447A1 (fr) * 2020-04-07 2021-10-14 Ramot At Tel-Aviv University Ltd. Dépôt électrophorétique simultané d'ensemble membrane-électrode
WO2023095889A1 (fr) * 2021-11-26 2023-06-01 公立大学法人大阪 Matériau actif d'électrode positive à base d'oxyde et utilisation de celui-ci

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000025378A1 (fr) * 1998-10-22 2000-05-04 Ramot University Authority For Applied Research & Industrial Development Ltd. Piles miniaturisees d'accumulation d'energie electrochimique
EP1424743A1 (fr) * 2002-11-29 2004-06-02 Kabushiki Kaisha Ohara Batterie aux ions de lithium contenant un électrolyte solide inorganique conducteur de ions Li
EP1770817A2 (fr) * 2005-09-29 2007-04-04 Air Products and Chemicals, Inc. Nanoparticules d'oxyde de métal à la surface lithiée pour des électrolytes de batteries au lithium
US20070212603A1 (en) * 2006-03-13 2007-09-13 Tel Aviv University Future Technology Development L.P. Three-dimensional microbattery
WO2008089110A1 (fr) * 2007-01-12 2008-07-24 Microazure Corporation Batteries tridimensionnelles et procédés de fabrication correspondants
US20080289365A1 (en) 2005-10-25 2008-11-27 Ohara Inc. Method for manufacturing glass-ceramics
WO2008149309A1 (fr) * 2007-06-07 2008-12-11 Koninklijke Philips Electronics N.V. Batterie à électrolyte solide et procédé de fabrication d'une telle batterie à électrolyte solide
US7662265B2 (en) 2000-10-20 2010-02-16 Massachusetts Institute Of Technology Electrophoretic assembly of electrochemical devices
US20100183915A1 (en) * 2009-01-21 2010-07-22 Tsuneaki Tamachi Electrochemical cell and method of manufacturing electrochemical cell
US7772800B2 (en) 2004-11-26 2010-08-10 Koninklijke Philips Electronics N.V. Energy system comprising an electrochemical energy source

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3643289B2 (ja) * 1999-04-30 2005-04-27 株式会社オハラ ガラスセラミックス複合電解質、及びリチウム二次電池
JP2001068149A (ja) * 1999-08-30 2001-03-16 Kyocera Corp 全固体リチウム二次電池
JP4773608B2 (ja) * 2000-09-28 2011-09-14 株式会社オハラ ガラスセラミックス及び温度補償部材
CN100508260C (zh) * 2003-10-14 2009-07-01 特拉维夫大学远景技术发展公司 电能储存器件及其制造方法
WO2007061928A2 (fr) * 2005-11-17 2007-05-31 Infinite Power Solutions, Inc. Batterie hybride en couche mine
US8691450B1 (en) * 2007-01-12 2014-04-08 Enovix Corporation Three-dimensional batteries and methods of manufacturing the same
EP2086046A1 (fr) * 2008-01-31 2009-08-05 Ohara Inc. Fabrication d'une batterie secondaire au lithium-ion
JP5211721B2 (ja) * 2008-01-31 2013-06-12 トヨタ自動車株式会社 全固体リチウム二次電池
JP2009181912A (ja) * 2008-01-31 2009-08-13 Ohara Inc 固体リチウム二次電池及びその製造方法
US8481357B2 (en) * 2008-03-08 2013-07-09 Crystal Solar Incorporated Thin film solar cell with ceramic handling layer
EP2272119B1 (fr) * 2008-03-27 2014-04-23 ZPower, LLC Séparateur d'électrode
JP2010108810A (ja) * 2008-10-31 2010-05-13 Ohara Inc リチウムイオン二次電池およびその製造方法
CN102270762B (zh) * 2010-06-03 2014-08-20 清华大学 锂离子电池电极浆料及应用该电极浆料制备的电极片

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000025378A1 (fr) * 1998-10-22 2000-05-04 Ramot University Authority For Applied Research & Industrial Development Ltd. Piles miniaturisees d'accumulation d'energie electrochimique
US6197450B1 (en) 1998-10-22 2001-03-06 Ramot University Authority For Applied Research & Industrial Development Ltd. Micro electrochemical energy storage cells
US7662265B2 (en) 2000-10-20 2010-02-16 Massachusetts Institute Of Technology Electrophoretic assembly of electrochemical devices
EP1424743A1 (fr) * 2002-11-29 2004-06-02 Kabushiki Kaisha Ohara Batterie aux ions de lithium contenant un électrolyte solide inorganique conducteur de ions Li
US7772800B2 (en) 2004-11-26 2010-08-10 Koninklijke Philips Electronics N.V. Energy system comprising an electrochemical energy source
EP1770817A2 (fr) * 2005-09-29 2007-04-04 Air Products and Chemicals, Inc. Nanoparticules d'oxyde de métal à la surface lithiée pour des électrolytes de batteries au lithium
US20080289365A1 (en) 2005-10-25 2008-11-27 Ohara Inc. Method for manufacturing glass-ceramics
US20070212603A1 (en) * 2006-03-13 2007-09-13 Tel Aviv University Future Technology Development L.P. Three-dimensional microbattery
WO2008089110A1 (fr) * 2007-01-12 2008-07-24 Microazure Corporation Batteries tridimensionnelles et procédés de fabrication correspondants
WO2008149309A1 (fr) * 2007-06-07 2008-12-11 Koninklijke Philips Electronics N.V. Batterie à électrolyte solide et procédé de fabrication d'une telle batterie à électrolyte solide
US20100183915A1 (en) * 2009-01-21 2010-07-22 Tsuneaki Tamachi Electrochemical cell and method of manufacturing electrochemical cell

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
AVERBUCH ET AL., J. POWER SOURCES, vol. 196, 2011, pages 1521 - 1529
CABALLERO A ET AL: "LiNi0.5Mn1.5O4 thick-film electrodes prepared by electrophoretic deposition for use in high voltage lithium-ion batteries", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 158, no. 1, 14 July 2006 (2006-07-14), pages 583 - 590, XP025085225, ISSN: 0378-7753, [retrieved on 20060714], DOI: 10.1016/J.JPOWSOUR.2005.09.018 *
CABALLERO ET AL., J. POWER SOURCES, vol. 158, 2005, pages 583 - 590
CORNI ET AL., J. EUROP. CERAM. SOC., vol. 28, 2008, pages 1353 - 1367
H. MAZOR ET AL., ELECTROCHEMICAL AND SOLID-STATE LETTERS, vol. 12, 2009, pages A232 - A235
H. MAZOR ET AL: "High Power Copper Sulfide Cathodes for Thin-Film Microbatteries", ELECTROCHEMICAL AND SOLID-STATE LETTERS, vol. 12, no. 12, 1 January 2009 (2009-01-01), pages A232 - A235, XP055020194, ISSN: 1099-0062, DOI: 10.1149/1.3240921 *
JEFFREY W. FERGUS: "Ceramic and polymeric solid electrolytes for lithium-ion batteries", JOURNAL OF POWER SOURCES, vol. 195, no. 15, 1 August 2010 (2010-08-01), pages 4554 - 4569, XP055020210, ISSN: 0378-7753, DOI: 10.1016/j.jpowsour.2010.01.076 *
KANAMURA ET AL., ELECTROCHEMICAL AND SOLID-STATE LETTERS, vol. 3, 2000, pages 259 - 262
KANAMURA ET AL., J. POWER SOURCES, vol. 97-98, 2001, pages 294 - 297
L. BESRA; M. LIU, PROGRESS IN MATERIALS SCIENCE, vol. 52, 2007, pages 1 - 61
LONG J W ET AL: "THREE-DIMENSIONAL BATTERY ARCHITECTURES", CHEMICAL REVIEWS, AMERICAN CHEMICAL SOCIETY, US, vol. 104, no. 10, 1 January 2004 (2004-01-01), pages 4463 - 4492, XP002570114, ISSN: 0009-2665, [retrieved on 20070819], DOI: 10.1021/CR020740L *
SUGIURA ET AL., FUNCTIONAL MATER. LETT., vol. 2, no. 1, 2009, pages 9 - 12
VAN DER BIEST; VANDEPERRE, ANN. REV. MATER. SCI., vol. 29, 1999, pages 327 - 352

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014102520A1 (fr) * 2012-12-31 2014-07-03 I-Ten Procede de fabrication de batteries tout solide en structure multicouches
FR3000616A1 (fr) * 2012-12-31 2014-07-04 I Ten Procede de fabrication de batteries tout solide en structure multicouches
CN104904039A (zh) * 2012-12-31 2015-09-09 I-Ten公司 制造多层结构的全固态电池的方法
KR20150103041A (ko) * 2012-12-31 2015-09-09 이-뗀 다중층 구조로 전-고체-상태 배터리를 제조하는 방법
US10454092B2 (en) 2012-12-31 2019-10-22 I-Ten Method for manufacturing all-solid-state batteries in a multilayer structure
KR102193422B1 (ko) * 2012-12-31 2020-12-21 이-뗀 다중층 구조로 전-고체-상태 배터리를 제조하는 방법
NL2011422C2 (en) * 2013-09-11 2015-03-16 Exergy Holding B V Electrolytic seperator, manufacturing method and system.
WO2015037990A1 (fr) 2013-09-11 2015-03-19 Exergy Holding B.V. Séparateur électrolytique, procédé et système de fabrication
WO2016184750A1 (fr) * 2015-05-21 2016-11-24 Basf Se Électrolytes en vitrocéramique pour batteries d'accumulateurs au lithium-soufre
US11967694B2 (en) 2018-05-07 2024-04-23 I-Ten Porous electrodes for electrochemical devices
CN114094187A (zh) * 2021-11-22 2022-02-25 珠海冠宇电池股份有限公司 一种非水电解液以及包括该非水电解液的电池
CN114094187B (zh) * 2021-11-22 2023-04-14 珠海冠宇电池股份有限公司 一种非水电解液以及包括该非水电解液的电池

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